1060 COHEN AND KARttISON : THE AC€ION OF AROXATIC AMIXES

XCVI .-The Action of Aromatic Arnines on Diacetyl- tartaric A nh y d 'ride.

By JULIUS BEREND COHEN, Ph.D., and WILLIAM HUDSON HARRISON, B.Sc., The Yorkshire College,

THE object of the present research was to prepare the aromatic amido-acids of tartaric acid, and by a comparison of the position iso- merides, for example, the three isomeric toluidotartaric acids, to determine the effect of such groups on the optical properties of the compounds in aqueous solution. In this manner, interesting evidence might be forthcoming for or against Guye's well-known theory.

Auwers (Annnnlen, 1896, 292, 173) has prepared the amido-acids of succinic acid by boiling the chloroform solution of succinic anhydride with the amine. This suggested the method of acting on the anhydride of tartaric acid with the amine. The diacetyl derivative of tartaric anhydride was selected, as it is readily prepared by boiling tartaric acid with an excess of acetyl chloride (Perkin, ~nncden, Supl. Band., 5, 2S7). The action of discetyltartaric anhydride on the amine did not give the result we anticipated. No amido-acid is produced, but the reaction results in the formation of a variety of other products ; among these, a series of new and very beautiful golden-yellow substances have been isolated, of which a brief account is given.

On boiling together equivalent molecules of aniline and diacetyl- tartaric anhydride dissolved in benzene and allowing the solution to cool, a glassy, amorphous substance separates, which could not be crjstallised.

That a reaction does occur between the anhydride and the amine, is shown by the fact that a considerable rise of temperature is produced by bringing the two compounds together. If the anhydride is dissolved in a large excess of aniline at a very gentle heat and the liquid allowed t o stand for several days, needle-shaped crystals gradually fill the liquid. The crystals were separated from the excess of aniline by dissolving the latter in ether, and, after recry stallisation from alcohol, gave the following result on analysis :

0.1957 gave 14.2 C.C. moist nitrogen a t 14' and 759 mm.

The crystals melt at 148", and on evaporating the aqueous solution todryness, aniline was given off and tartaric acid remained. The substance is therefore monoacetyltartranilide. *hen diacetyltartaric anhydride and aniline are heated together at 150°, water aud acetic acid are given off and a solid, yellow mass results. Prom this, alcohol extracts an uncrystallisable oil, acetanilide, a yellow crystalline compound and a small quantity of tartranilide, leaving a yellowish residue consisting

N = 8.53. C,,H,,N,O, requires N = S.2 per cent.

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ON DIACETYLTARTARIC ANHYDRIDE. 1061

mainly of tartranilide and some of the yellow compound. On adding a little water to the alcoholic extract, the whole of the yellow com- pound and the tartranilide are precipitated, and the two latter may be separated by extraction with benzene, which dissolves out the yellow compound only.

The tartranilide was recrystallised from alcohol and gave the following result on analysis :

0.2117 gave 16.7 C.C. moist nitrogen at 10.5Oand 751.5 mm. N = 9.33. C,,H,,jN,O, requires N = 9.3 per cent.

The quantity of the yellow compound prepared in this way was very small, and the proportion of aniline and the anhydride, as well as the temperature, were varied in order to obtain an improved yield. Tartranil and tartranilide were also heated with aniline with the same object. The best result was obtained by heating 10 grams of diacetyltartaric anhydride and 8.5 grams of aniline at 150' for about threequarters of an hour.

The yellow compound was recrystallised from benzene, from which it separates in the form of golden, spindle-shaped crystals.

The following results were obtained on analysis :

I. 0.2002 gave 17.5 C.C. moist nitrogen at 14" and '759 mm. N = 10.28. 11.0.1703 ,, 15.1 ,, ,, at 14.5 ,, 759.5 mm. N = 10.41.

C,,H12N,0, requires N = 10 per cent. C,&4,N,O, 9 , N = 1 0 * 6 9 ,

The substance decomposes above 200" without melting. It is insoluble in caustic soda, but on prolonged boiling it gradually dissolves, aniline being evolved and the yellow colour disappearing. The solution contained neither tartaric nor dioxytartaric acid.

From the analysis and properties of the compound, the Substance will probably have one of the following formulae :

Until we have succeeded in finding a more direct method of preparing the substance, we shall postpone any further discussion of the formula.

Paratoluidine and P-naphthylamine produce similar yellow, crystal- line compounds to the above, the only difference being that the paratoluidine compound is of a deeper tint. Orthotoluidine and a-naph- thylamine, under similar conditions, yield products which we have not yet succeeded in purifying. An analysis of the paratoluidine derivative gave the following

result : VOL. LXXI. 4 B

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1082 LEAN AND LEES : INTERACTION O F ETHYLENIC CHLORIDE,

0,1484 gave 12 C.C. moist N a t 16.5' and 768 mm. N = 9.52 per cent. C,,H,,N,O, requires N = 9.5. C,,H,,N203 ,, N = 9.1.

A molecular weight determination in boiling benzene gave the

0.0675 in 19.6 of benzene raised the boiling point 0.03'.

following result :

M. W= 297.6. C,,H,,N,O, = 308.

By the action of P-naphthylamine on diacelyltartaric anhydride, four principal compounds are formed, which are separated as follows. The product of the reaction is first extracted with benzene, the benzene solution is then distilled and the residue extracted with water which dissolves aceto-P-naphthylide and leaves a very small quantity of the yellow compound.

The latter was analysed with the following result :

0.0687 gave 4 C.C. moist N a t 14" and 756 mm. N = 6.82 per cent. c24H1,N202 requires N = 7*6 per cent, c24H16N203 9 9 N = 7 * 4 9 ,

The portion insoluble in benzene was extracted with water, The substance insoluble in water was tartaric P-naphthylide, it was converted into the acetyl derivative, recrystallised from glacial acetic acid, and analysed.

0.1 104 gave 5.7 C.C. moist N at 14" and 755 mm. N = 5.96 per cent. C,,H,,N,O, requires N = 5.78 per cent.

The compound, which was not dissolved by benzene but, dissolved in water, is probably tartaric naphthylamil, that is, the naphthyl- amine analogue of tartranil. It gave on analysis the following result :

0.1742 gave 8.5 C.C. moist N at 12" and 749 mm. N = 5-72 per cent, C,,H1204N requires N = 5.42 per cent.

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